Extreme pressure complex grease



United States Patent 3,219,581 EXTREME PRESSURE COMPLEX GREASE Martin M. McCormick, Chicago, and John A. Lundquist, Park Forest, 1., assiguors to Sinclair Research, Inc., Wilmington, Del., a corporation of Delaware No Drawing. Filed Feb. 12, 1962, Ser. No. 172,774 Claims. (Cl. 252-336) This invention relates to an improved extreme pressure lubricant and more particularly to agents which impart extreme pressure, increased load carrying capacity and anti-wear properties to greases and gear lubricants.

It is well known that the high pressure occuring in certain types of gears and bearings may cause a film of lubricant to rupture with consequent damage to the machinery. It has been shown that base lubricants such as mineral oil and/or synthetic oil can be improved with regard to their protective efiect particularly on rubbing surfaces by the addition of certain substances, so that excessive wear, scufiing and seizure, which normally follow a break in the film of lubricant, can be prevented even under very unfavorable pressure and speed conditions. Lubricants possessing this highly desirable property are called extreme pressure lubricants.

Extreme pressure lubricants have found extensive use as gear lubricating fluids, such as in the lubrication of gear transmissions of trucks and other vehicles. The lubrication of gears demands lubricants of special qualities particularly high lubricity and high film strength. When a lubricant is compressed between two moving metallic surfaces, high film strength is necessary to prevent the escape or squeezing out of said lubricant from between said surfaces, with consequent welding. The extreme pressures to which such lubricants are subjected when compressed between the gear surfaces cause a rise in internal heat which is augmented by any friction generated by lack of point-lubricity. It has been found that petroleum lubn'cating oil fractions alone are unsatisfactory in that they do not have required high lubricity and high film strength and consequently allow scoring and welding of gears on continued use, together with oil breakdown because of heat generated due to high friction, etc. This is particularly true with more or less highly refined petroleum oil fractions which tend to have lower lubricity than less highly refined fractions.

Many types of additives have been prepared and added to extreme pressure lubricant formulations for the purpose of augmenting film strength, lubricity and other desired characteristics. Fatty oils and fatty acid esters, for example, have been added in various amounts and combinations to hydrocarbon oil fractions, particularly for the purpose of furnishing oilness, that is to say, high lubricity. It has also been found that when sulfur-containing compounds are added to extreme pressure lubricants, film strength is somewhat increased, and recent formulations have combined ester additives with sulfur by sulfurizing said esters to provide both lubricity and film strength of high degree. Still more recently, it has been discovered that the use of phosphorus in combination with the sulfur-containing ester additives has further augmented desired film strength to a level of highly satisfactory performance. Thus, oils and fatty esters may have incorporated therein phosphorus and sulfur by reaction with any one of a number of phosphorus sulfide compounds, such as phosphorus sesquisulfide. The increased 3,219,581 Patented Nov. 23, 1965 performance of phosphorus and sulfur-containing esters as additives for extreme pressure lubricants, when compared with sulfur-containing esters as additives for extreme pressure lubricants, may be seen in that the former are effective for transmissions operating at both low speed and high torque, and at high speed and low torque, whereas esters which have only been sulfurized and which are considered suitable extreme pressure additives exhibit in the extreme pressure lubricants satisfactory performance only under conditions of low speed and high torque.

It has now been discovered that extreme pressure and anti-wear lubricants can be obtained by incorporating into a base lubricant the condensation product of a polyhalogenated cyclic conjugated diene and an unsaturated acid, acid derivative or olefin. More particularly, the present invention resides in an extreme pressure lubricating composition comprising a major amount of base lubricating oil and a minor amount of the condensation product of a polyhalogenated cyclic conjugated diene and an unsaturated acid, acid derivative or olefin. The extreme pressure additives of the present invention have the following structural formula:

in which X is a halogen having an atomic weight of from about 35 to about Y is selected from the group consisting of halogens having an atomic weight of from about 35 to about 80 and hydrogen; R, R and R are selected from the group consisting of hydrogen and hydrocarbon radicals (aliphatic, straight or branched, cycloaliphatic or aromatic, saturated or unsaturated, substi tuted or unsubstituted) of from 1 to about 28 carbon atoms; R is preferably hydrogen or a hydrocarbon radical of from 1 to 10 carbon atoms and R" and R are preferably hydrogen; Z is selected from the group consisting of hydrogen and lower alkyl radicals; in is an integer of from 0 to 28, preferably 0 to 12; n is an integer of from 0 to 1 and where the sum total of R, R", R and (CH (COOZ) has a minimum of 2 and a maximum of 36 or more carbon atoms. When n is 1 the extreme pressure additive can be in the form of an alkaline metal salt, e.g. alkali metal or alkaline earth metal salts, preferably the alkaline earth metal salt calcium. These compounds and their alkaline metal salts are particularly effective in raising the extreme pressure level of metal soap thickened greases made with a calcium acetate-soap thickener system, as well as unusually high mean Hertz load and weld point in homogeneous fluid lubricants made with low mol ratio calcium acetate/calcium soap.

It is known that by heating unsaturated carboxylic acids or their esters with conjugated dienes condensation products are obtained according to the well-known Diels-Alder reaction, the so-called 1:4 addition. The Diels-Alder reaction is an example of a stereospecific cisaddition, thus substituents in the dienophile compounds retain their original orientation. In the reaction of a dienophile with a cyclic diene two modes of addition are possible, as formulated, for example, by the reaction of cyclopentadiene with maleic anhydride, although actually one product is obtained, the endo form. These reor bleached fatty acids.

actions may be exemplified by the following stereochemical structures:

o I o f; l

h 0 (ENDO) C (EXO) Therefore, the possibility of optical and steric isomerism in compounds of the present invention will be obvious to those skilled in the art. The additives of the present invention are named with reference only to the position of the substituents, and it is intended to include in these designations any or all ofthe possible optical or steric structural isomers comprehended thereby.

Theadditive is prepared by condensing the polyhalogenated conjugated diene, reacting as dienes, and the-unsaturated acid, their acid derivative or olefin, reacting as dienophiles, under Diels-Alder condensation conditions. The preferred dienes are the chlorine substituted cyclopentadienes and cyclohexadienes. The unsaturated acids, acid derivatives, or olefins may contain from about 4 to 50 carbon atoms, butpreferably they contain from 4 to 36 carbon atoms. The dienophile compouind may also contain hydroxy, oxygen, nitrogen, sulfur or phosphorus substituents.

The condensation may be carried out with fatty acid mixtures of different compositions, e.g. products which only contain unsaturated fatty acids having one double bond, oleic acid, or products which contain both unsaturated acids with one double bond and with two'or more double bonds, such as linoleic acid, linolenic acid, etc. in widely'ranging proportions. Saturated fatty acids may also be present. They may further contain unsaturated hydroxy fatty acids and dimers and polymers of unsaturated fatty acids. It is possible to start from the free fatty acids and from their esters. Suitable starting materials are, for example, animal oils and fats, e.g. the so-called destruction fats (obtained from waste material of animal origin): bone fat, yellow grease, brown grease, whale oil and fish oils, vegetable oils and fats, such as palm oil, soya bean oil, cotton seed oil, sun flower seed oil and linseed oil, and unsaturated, synthetic fatty acids, fatty acids, fatty acids obtained from the abovementioned oils and fats and mixtures of two or more of the above-mentioned products. Said oils, fats and fatty acids may be partly hydrogenated, oxidized and/ or polymerized, also, both unrefined or refined, e.g. distilled When distilled fatty acids are used a slightly smaller amount of catalyst, if it be used,

will suflice to achieve the same result as with non-distilled ly, the polyhalogenated cyclic conjugated dienes and the unsaturated acids, acid derivative, or olefins, containing from about 4 to '50 carbon atoms. The preparation of t e a d tive is subject to variation as the relative amounts of the respective reactants employed. Generally, the diene compound will be employed in molar excess relative to the unsaturated acids, acid derivative or olefin, mole ratios of about 1:1 to about 10:1 being generally satisfactory. The reaction may be accelerated and/or its course controlled by the application of heat to the reaction mixture, or by conducting the reaction in the presence of a suitable condensation catalyst, or by the application of both heat and a condensation catalyst. The reaction temperature is not critical in that it may vary over a range of temperature. The present starting materials can be adducted at temperatures between C.

to about 200 C. Excessively high temperatures may cause some decomposition and are therefore undesirable. The use of lower temperatures merely reduces the rate of reaction. Temperatures between about C. and about C. are preferred. The reaction time will normally vary between about 2 to about 24 or more hours, depending on the temperature employed. The use of more elevated temperatures substantially reduces the length of time. Excess time is not harmful since after reaction has taken place the product is reasonably stable. Less time than is required to complete the reaction only results in having some unreacted components in the reaction mixture, but does not affect the obtaining of the desired product.

Catalysts have been found generally unnecessary in this reaction; if desired, however the process may be accelerated by the addition of condensation catalysts. Suitable condensation catalysts include, among others, acids, acid salts, and substances which generate acid in :situ. The acidic catalysts, particularly the strongly acidic catalysts are employed in moderate amounts of up to about 10% of the weight of the reactants.

Solvents and diluents may advantageously be employed in many cases.- Where temperature control is desired, the use of a solvent boiling at approximately the tem' perature of the reaction may be used. The solvents useful in the preparation of the additive of the present invention are many; it being only desired that such solvent be not reactive under the conditions utilized and that its solvency characteristics be such as to at least partially dissolve the reacting components. Hydrocarbon solvents, both aliphatic and aromatic, chlorinated solvents, alcohols, ethers, esters and the like are suitable. Specifically, benzene, toluene, Xylene, dioxane, hexane, heptane, octane, carbon tetrachloride, chloroform, o-dichlorobenzene, ethylene dichloride, ethanol, ethylene glycol, diethylether, dipropyl ether, tetrahydrofuran, ethyl acetate, etc. are useful solvents in the present process. Pressure. techniques may also be utilized to prepare the extreme pressure additive of the present invention. Thus the reactants can be placed in a pressure vessel and reacted under the pressure generated by the vapor of the reactants and solvent, if the latter be utilized. Since the re,

action involves the formation of 1 mole of product per 2 moles reactant, the application of pressure may be desirable. The use of a nitrogen atmosphere, a stabilizer, such as propylene oxide and an antioxidant such as hydroquinone is not essential, but is useful in minimizing side reactions. The reaction between the polyhalogenated cyclic diene and the unsaturated component may be effected in either a batchwise, an intermittent or a continuous manner.

The following examples are illustrative of the method for preparing the additive of the present invention and are not to be considered as limiting.

EXAMPLE I 1,4,5,6,7,7-hexachloro-3-0ctyl-bicyclo(2,2,1 )-5-heptene-2-methyl caprylate (GHzhCOOCHs [1,4,5,6,7,T-hexachloro3oetyl-bieyclo (2,2,1) -5-heptene-2- methyl caprylate] This product analyzed as follows:

Theory Experimental Molecular Weight 570 502 Chlorine, Percent 37. 43 37. 2 Acid No 1. 37 Sapom'fieation No 143 Bromine No. 2. 5

EXAMPLE II 1 ,4,5,6,7,7-lzexach loro-bicyclo (2,2,1 -5 -h e ptene-Z-methyl formate 90 grams (1 mole) of methyl acrylate and 840 grams (3 moles) of 'hexachlorocyclopentadiene were refluxed in 200 grams of xylene at 150 C. for '18 hours under an atmosphere of nitrogen. The reaction product was vacuum topped to remove the excess diene and xylene solvent and filtered to give 343 grams (94% yield) of the adduct. The reaction may be exemplified by the following:

[1,4,5,6,7,7-hexachlorobicyclo (2,2,1) -5 heptene-2- methyl formate] EXAMPLE III 275 grams of ADM adencene A-Sl, comprising mixed G -C alpha olefins as major constituents and having the following composition.

Carbon chain: Weight percent C12: 7 C 16 C16: 40 C 30 c 7 and 820 grams (2.9 moles) of hexachlorocyclopentadiene were stirred for 23 hours at 170 C. under a nitrogen atmosphere. The reaction mixture was vacuum topped to remove the excess diene and filtered to give a 576 gram yield of the adduct analyzing as follows:

l lgrams (5.0 moles) of Emery 680 fatty acid, a straight chain fatty acid of vegetable origin and having the following characteristics:

Acid No 240 Saponification No. 240 Iodine value 62 Average mol. weight (average C carbon chain length alkyl carboxylic acid containing unsaturated components) 233 and 3825 grams (14 moles) of hexachlorocyclopentadiene were mixed and stirred for 18 hours at C. under a nitrogen atmosphere. The reaction product was vacuum topped to remove excess diene and filtered giving 2446 grams of the adduct. The product analyzed as follows:

Theory Experimental Chlorine 40. 7 38. 5 Acid No 94.7 Saponification N0 453. 3

The soap-forming carboxylic acids that may be used in this invention are the saturated and unsaturated, naturally occurring or synthetic grease-making fatty acids that are commonly known in the art and contain about 7 to 30 carbon atoms. Thus the mixed salt-soap thickened grease can be formed by the neutralization with a metal base of a low molecular weight and a higher molecular weight carboxylic acid, for instance high molecular weight acids and intermediate molecular weight acids and combinations of the same. Therefore, the mixed salt-soap thickened grease may be formed from either a combination of (1) a low molecular weight acid and a high molecular weight acid, or (2) a low molecular weight acid and an intermediate molecular weight acid, or (3) a low molecular weight acid, an intermediate molecular Weight acid and a high molecular weight acid. In general, the higher fatty acids have from about 12 to 30 carbon atoms, preferably about '12 to 22 carbon atoms per molecule, and have saponification values of from about 300 to 150. The fatty acids normally used in the manufacture of conventional greases, particularly the saturated acids, are preferred. Suitable fatty acids include lauric, myristic acid, palmitic acid, stearic acid, the various 'hydroxy stearic acids, oleic acid, arachidic acid, behenic acid and the like. Naturally occurring fatty acids such as fish oil acids, tallow acids, which contain chiefly stearic acid, coconut oil acids, castor oil, etc. may also be utilized directly or after hydrogenation to decrease any undesirably high degree of unsaturation. Mixtures of these high molecular weight fatty acids, e.g. hydrogenated fish oil acids with oleic acid, in any proportions, are also operable, as are fractions obtained by distillation, extraction or crystallization.

The intermediate molecular weight monocarboxylic acids are those straight-chain, saturated fatty acids having from about 7 to 12 carbon atoms. Operable intermediate molecular weight carboxylic acids are exemplified by:

Caprylic, pelargonic, and capric acids are preferred. The intermediate molecular Weight carboxylic acids of even carbon chain lengths are normally obtained by processing from naturally-occurring materials such as coconut oils. Pelargonic acid is obtained as a by-product in the production of azelai-c acid by the ozonolysis of oleic acid.

The low molecular weight acid can be glacial acetic acid or an aqueous solution of acetic acid. The concentration of acid in the solution often varies fro-m about 60 to 99.9 weight percent, and is preferably about 80 weight percent. The use of a substituted acetic acid is not excluded, where such modification may be desirable. For example, chloroacetic acid may be used to modify the structure of a grease made in accordance with the invention.

The metal component of the thickener system of the invention is used in a form which can combine chemically with carboxylic acids to form salts or soaps. 'Ordinarily the metal hydroxide is used. The choice of metal component depends to a certain extent on the use to which the multiple salt and soap thickener of the invention is to be put. The alkaline earth metal hydroxides or carbonates such as those of calcium, barium and strontium are useful for many purposes of the invention. Calcium hydroxide or hydrated lime is especially preferred.

The calcium acetate to fatty soap ratio in the greases is generally from about 0.5 to :1 and preferably from about 1 to 6: 1. During processing the maximum temperature is about 300 to 350 F., preferably about 320 to 350 F. The calcium acetate and fatty soaps utilized in this invention may be prepared by any suitable convenient process. The constituents can be preformed, ifdesired, i.e. the acetate and soaps prepared in the absence of the lubricating oil base.

The lubricating oil used may be either a naturally occurring mineral oil or a synthetic oil of lubricating viscosity. The lubricating oil viscosity will preferably be within a range of from about 35 to 150 SUS at 210 F. In addition to diester synthetic lubricants, e.g. di(2-ethyl hexyl) sebacate, other forms of synthetic lubricating oils such as complex esters (prepared by the reaction of alcohols, dibasic acids and glycols), formals, polymerized olefins, ether esters, ester ethers and the like may be used. It is generally desired that the grease composition contain about 5 to 30 percent by weight of the calcium acetatefatty soap thickener but in any event is sufficient to give a product of grease consistency. Usually, the function or use of the grease will determine the amounts of constituents utilized.

In the preparation of these mixed salt-soap thickened greases any suitable procedure may be used, for instance, a coneutralization, pre-forming or step-Wise method. In the coneutralization method, a mixture of the low and high and/ or intermediate molecular Weight acids is neutralized with a suitable base, particularly the hydroxide and/ or carbonate of the desired metals. This coneutralization step is generally carried out in a grease kettle in situ, in the liquid menstruum to which the complex thickener is to be applied in actual use. For example, the mixed acids may be coneutralized in a portion or all of the lubricating oil forming the dispersant of a grease to be thickened by the mixed salt-soap thickener. Coneutralization is possible in cases in which the salts have the same metal constituent, and the menstruum is inert under the conditions of saponification or neutralization. The coneutralized material may be heated to temperatures of about 250 to 500 F., preferably less than about 350 F. in order to dehydrate the product. The extreme pressure additive can be added in the neutralization step, but when the extreme pressure agent is in the form of the acid or ester prior to neutralization it will form the metal salt. When the salts of the adduct are formed in situ they are part of the thickener system.

The mixed salt-soap thickened grease may also be prepared by separately preforming at least a portion of the high and/ or intermediate molecular weight carboxylic acid salt, intimately mixing this salt with the low molecular Weight salt and then heating, if necessary. This method is less desirable than coneutralization in situ and is perhaps most useful from a practical standpoint When different metals are employed in forming the different salts.

In the step-wise method the high molecular weight acid is melted in the base oil and in the presence of the metal base and then the low and/or intermediate weight acids are added and the mixture is allowed to react at a temperature suflicient to render the grease substantially anhydrous.

The grease of the present invention may be prepared by using the normal type of grease-making equipment. One of the most important advantages in terms of cost of the grease is that it can be made conveniently in -a steam jacketed kettle at a moderate kettle temperature in the order of about 300 or 320 to 350 F. In one process of manufacture, the fatty components and excess hydrated lime slurried in all or a part of the oil base can be first charged to the kettle at a convenient temperature such as P. Then the acetic constituent such as acetic acid is charged to the kettle and the temperature is slowly raised in the saponfication step during a period of from about 30 to 60 minutes to a temperature of from about 200 F. to 280 F. Dehydration is then effected by raising the temperature to about 300 to 350 F., preferably about 320 to 350 F. After the dehydration has been effected the greases are finished by reducing the temperature and any remaining base oil can be included. Also, the mixture may be sent to a colloid mill. The colloid milling operation is subject to considerable flexibility through control of the variables of inlet temperature, rate of throughput and mill clearance, with decrease in all three tending to increase the yield or the thickening effect. The colloid mill clearances ordinarily vary from about 0.003 to 0.40 inch, preferably about 10 The data in Table II are presented to shown that the beneficial effects of the adducts of the present invention on extreme pressure properties are specific to calcium acetate-soap type greases. Part of the hydrogenated castor pass milling may be employed. oil in the lithium grease composition, prepared in the con- The additives of the present invention have been found ventional commercial manner with in situ saponification effective in the base lubricants in amounts ranging beof the fatty component in the mineral oil followed by tween about 0.1 to 20 weight percent, preferably between dehydration at 320-340 F., was substituted with the Zto weight percent. adduct of Example I giving no appreciable increase in The following data serve to illustrate the effectiveness 10 the T imken E.P. value. of the additive of the present invention in low mol ratio calcium acetate-fatty soap based greases. TABLE II" LITHIUM BASE GREASES Table I presents comparative data showing the im- F t C aty omponent: provernents obtained with a calcium acetate soap thick Hydrogenated Castor Oil m0 7 ened grease made with 0.5/1 weight ratio acetic acid/ AdductofExampleI 25 fatty component with and without the addticts from Examples I and II above. The grease compositions were Sample No 4 5 prepared by adding 1 pound of the condensation product of Example I with 1 pound of melted tallow acids to 0.9 Lithium Soap pound of hydrated lime slurried in mineral oil. These tgg fiig constituents were maintained in a steam heated kettle AS131 Perlitetationst at 95 F. for about 15 minutes, after which 1 pound of affi glacial acetic acid was added to the kettle. The tempera- 4 wcg p ture was1 ncilaintgingd for another 15 m(i1nute;4b3ef3oi hii at 52 9 c t g l was app ie an t e temperature raise to 2 5 H0811 lance 22d held 1ftilr aboultl hours to degigdgatehthe IIIIITXUJIE. i gfig fiigg fi'ii igggfitfi fiffffffflfEff??? a a t S a e w n ater eac ing, ercent eny p nap y amine we: e t e tem ASTM Dropping Point, OFM perature decreased to about 286 F. The grease was aly pressure Bleed, Percent lowed to stand overnight and the next day the grease x gg gg gg g -gfi E Fa Leakflsegramsn was milled through a No. 1 Charlotte colloid mill at p at 25 l/sicsuhn" Poises at 100 l/secs 0 005 clearance, 100 F and 2 lbs /minute rate to 0b 4 Ba Wear 1800 with 1300 F 5kg our, mm. mm a dark, smooth, uniform, buttery product. 5021i Using the adducts of Examples I and II the results in Mean Hertz Load, kg Table I show a large increase in load carrying capacity kg as measured by the Timken E.P. Test, approximately a Tmken EP: passlbs 26% and 32% increase in the mean Hertz loads, and about a 89% and 12% increase in the weld points using MIL-G409? O11 Sepammn Test h shen 4 Ban Test- Also the greas P The data in Table III are presented to show the comparations with the adducts from Examples I and II included five results of the addition of the adduct of Example III in show improved resistance to washout in the Water Spray 40 33; t ydr us ca u and calcium a ta L {LS8 "T62. Test at 175 F. Other important physical properties a such as dropping (melting) point, anti-wear, low tem- The results show a large improvement in E.P. properties perature viscosity, bleed rate, and mechanical stability as measured by the Timken test in the calcium acetate were not adversely affected. base grease containing the additive compared to only a TABLE I Formulation, Wt. Percent:

Glacial Acetic Acid 5. 25 6. 25 0. 25 Tallow Acids 10. s. 25 9. 36 Adduct of Example I. 6. 25 Adduct of Fram II- 3.12 Hydrated Lime 4. 5. 62 6. 10 Mid-Continent Oil v.1. 95, 430 sUs/i00 F 78.80 75. 23 74. 77 Phenyl Alpha Naphthylamine 0. 50 0. 40 0. 40

Sample N n 1 2 3 Moisture, percent 0. 10 0.10 0. 30 Free CaO, percent. 0.17 0. 37 0. 43 ASIM Penetrations:

Unworked 247 323 295 Worked 272 are 360 100,000-ASTM 345 383 360 100,000Navy 322 361 351 4 Hour Shell Roll:

RT, percent Change 27. 6 19. 6 235 F., percent Change -l9. 2 15. 6 96 Hour Shell Muller: ASTM Penetration Change 54 58 Water Spray:

RT, percent Loss 1. 4 1. 2 1. 7 175 F., percent Loss 46. 4 13. 5 14. 6 ASTM Dropping Point, F. 500+ 500+ 500+ RIA Pressure Bleed, percent 1. 3 2. 7 1. 8 Wee! Bearing 660 r.p.m. 250 F.. L 2. 7 0. 8 1. 2 Apparent Viscosity at 0 F.:

Poises at 25 1/secs 2, 700 2, 200 2,800 Poises at 100 1/secs 580 1, 500 1, 750 4 Ball Wear 1800 r.p.rn. F.. 10 kg. 1 hour, mm. scar. 0. 27 0.30 0. 27 4 Ball EP:

Mean Hertz Load, kg 26. 9 33. 9 35. 7 Wel kg 158 300 17s Timken EP.: Pass, lbs 9 35 40 lMIL-G-IOQZ LA Oil Separation Test.

slight increase in Timken load using the same percentage of additive in conventional lithium and calcium greases. There were essentially no adverse effects of the adduct as an additive on other physical properties of the base greases.

12 The test data in Table IV show a 35 lb. Timken value, a high mean Hertz load and Weld Point in the 4 Ball EP Test, a low 4 Ball Wear Test, and a high Base Number indicating reserve alkalinity or bufifer eifect of the acetate-adduct salt system at a mildly alkaline initial pH.

TABLE III Base Grease Type Calcium Acetate Lithium Hydrous Calcium Sample No 1 6 7 8 9 10 Adduet of Example III Additive percent None 5. 5 None 5. 5 No 5. ASTM Penetrations: 7 He 5 Unworked 247 252 268 291 366 383 272 289 278 287 276 385 345 355 806 313 322 332 4 Hour Shell Roll:

RT, percent change +2 4 cant using a 1/1 molar ratio calcium acetate/calcium salt of the adduct of Example IV was prepared by adding 2 pounds of the adduct of Example IV to 1.29 pounds of hydrated lime slurried in 9 pounds of mineral oil in a steam heated kettle at 110 F. 1 pound of glacial acetic acid was added in increments over a 5 minute period. The components were mixed for minutes and heat applied to bring the kettle temperature to 345 F. The mixture was held at a temperature of 345 F. for about 3 to 4 hours in order to dehydrate it, and then the steam shut off to allow the gases to cool. When the temperature reached about 250 F., 0.065 pound of phenyl alpha naphthylamine was added. The kettle contents were allowed to cool overnight and the grease was milled in a colloid mill at 0.005 clearance, at ambient temperatures to obtain a smooth, semi-fluid product.

TABLE IV Mol ratio acetate soap 1/1 Fatty component of soap: Adduct of hexachloropentadiene and Emery 680 fatty acid of Example IV. Tests on adduct:

Acid No. 94.7 Saponification No. 453.3 Chlorine, wt. percent 38.5 Equivalent weight 120 Sample No. 11 Calcium acetate, percent 10.3 Calcium soap, percent 18.3 Moisture, percent 0.6 Free CaO, percent 0.9 Phenyl alpha naphthylamine, percent 0.5 Mid-Continent oil, VI 95, 430 SUS/ 100 F. percent 69.4 ASTM D-644:

Base No. 72.3 Initial pH 8.1 Timken EP: Pass, lbs. 4 Ball EP:

Mean Hertz load 69.5 Weld point, kg. 355 4 Ball Wear, 1800 r.p.m., 130 F.: 10 kg. 1 hour,

mm. scar 0.32 SlL Mobileometer (125 g.), sec. 24

235 F., percent change +12. 8 96 Hour Shell Muller: ASTM Penetration Change. +34

Water Spray:

RT, percent loss 1. 35 175 F., percent loss 46. 4 ASTM Dropping Point, F 500+ RIA* Pressure Bleed, percent 1. 3 Wheel Bearing 660 rpm. 250 F.: Leakage, grams 2. 7 Apparent Viscosity at 0 F.:

Poises at 25 1/secs 2, 700 Poises at 100 1/secs 1, 580 1, 450 4 Ball Wear 1,800 r.p.m. 0 kg. 1 hour mm. scar. 0.27 0.29 4 Ball EP:

Mean Hertz Load 26. 9 31. 4 22, 7 Weld, k 158 158 112 :I Timken EP: Pass, lbs 9 35 6 15 3 9 MIL-G-10924A Oil Separation Test. A stable, homogenous, mineral 011 base semi-fluid lubri- W l i 1. A lubricating composition consisting essentially of a major amount of base oil of lubricating viscosity thickened to a grease consistency with calcium acetate and a calcium soap of a saponifiable fatty component, said acetate to said fatty soap being in a mol ratio of about 0.5 to 10:1 and a minor amount sufiicient to improve extreme pressure characteristics of the calcium salt of a material selected from the group consisting of a compound having the following structural formula:

in which X is a halogen having an atomic weight of from about 35 to about 80; Y is selected from the group consisting of halogens having an atomic weight of from about 35 to 80 and hydrogen; R, R" and R' are selected from the group consisting of hydrogen and alkyl radicals of from 1 to about 28 carbon atoms; in is an integer of from 0 to 28; and where the sum total of R, R", R and (CH (COOH) has a minimum of 2 and a maximum of 36 carbon atoms.

2. The lubricating composition of claim 1 wherein the oil of lubricating viscosity is a mineral lubricating oil.

3. The lubricating composition of claim 2 wherein the calcium salt is formed in the base oil.

4. The lubricating composition of claim 1 wherein the extreme pressure compound is present in amounts between about 0.1 to 20 weight percent.

5. A lubricating composition consisting essentially of a major amount of base oil of lubricating viscosity thickened to a grease consistency with calcium acetate and a calcium soap of a saponifiable fatty component, said acetate to said fatty soap being in a mol ratio of 1 to 6:1 and between about 2 to 10 weight percent sufficient to improve extreme pressure characteristics of the calcium salt of a material selected from the group consisting of a compound having the following structural formula:

X o R XC C-R H XCY (g XC R in which X is a halogen having an atomic weight of from about 35 to about 80; Y is selected from the group consisting of halogens having an atomic Weight of from about 35 to about 80 and hydrogen; R, R and R are selected from the group consisting of hydrogen and hydrocarbon radicals of from 1 to about 28 carbon atoms; In is an integer of from O to 28; and where the sum total of R, R", R' and (CH (COOH) has a minimum of 2 and a maximum of 36 carbon atoms.

6. The lubricating composition of claim 5 wherein the oil of lubricating viscosity is a mineral lubricating oil.

7. The lubricating composition of claim 5 wherein the calcium salt is formed in the base oil.

(CHQEUC O OH) 8. The lubricating composition of claim 1 wherein R, R and R' are hydrogen and m is an integer of O to 12.

9. The lubricating composition of claim 1 wherein R is an alkyl radical, R" and R' are hydrogen and m is an integer of from 0 to 12.

10. The lubricating composition of claim 9 wherein R has from 1 to 10 carbon atoms.

References Cited by the Examiner UNITED STATES PATENTS 2,735,815 2/1956 Morway 25239 2,771,423 11/1956 Dorinson 252-54.6 2,846,392 8/1958 Morway et al. 252-40.7 X 2,971,913 2/1961 David et a1. 25254.6 X 3,072,571 1/1963 Jordan et a1 252-54.6 3,688,911 5/1963 Staifin et al 25254.6

Het Acid, by Hooker Electrochemical Co., Bulletin No. 40, New York, 1952, 13 pages.

20 DANIEL E. WYMAN, Primary Examiner.

JOSEPH R. LIBERMAN, Examiner. 

1. A LUBRICATING COMPOSITION CONSISTING ESENTIALLY OF A MAJOR AMOUNT OF BASE OIL OF LUBRICATING VISCOSITY THICKENED TO A GREASE CONSISTENCY WITH CALCIUM ACETATE AND A CALCIUM SOAP OF A SAPONIFIABLE FATTY COMPONENT, SAID ACETATE TO SAID FATTY SOAP BEING IN A MOL RATIO OF ABOUT 0.5 TO 10:1 AND A MINOR AMOUNT SUFFICIENT TO IMPROVE EXTREME PRESSURE CHARACTERISTICS OF THE CALCIUM SALT OF A MATERIAL SELECTED FROM THE GROUP CONSISTING OF A COMPOUND HAVING THE FOLLOWING STRUCTURAL FORMULA: 